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United rates VAT DYESTUFFS CONTAlNING HALOPYRINH- DINE SUBSTITUENTS Max Staeuhle, Basel, Switzerland, assignor to Ciba Corporation, a corporation of Delaware No Drawing. Filed Nov. 16, 1960, Ser. No. 69,553

Claims priority, application Switzerland Nov. 20, 1959 7 Claims. (Cl. 260--256.4)

This invention provides valuable new vat dyestuffs which correspond to the general formula it 5.2 n in which A represents the radical of a vat dyestufi (as defined below), or of an intermediate product convertible into such dyestulf, X represents a chlorine atom or an alkyl group, Z represents a hydrogen or chlorine atom, and n is the whole number 1, 2 or 3.

The term vat dyestuffs is used herein to denote those vat dyestufis which can be converted by reduction into a leuco-form or vat, possess a better afiinity for natural or regenerated cellulose fibers than in the non-reduced form, and can be reconverted by oxidation into the original chromophoric system.

As suitable vat dyestuifs there may be mentioned more especially those of the anthraquinone series, for example, those which contain an unchanged 9:10-dioxo-anthracene ring, and also anthraquinones which contain fused-on carbocyclic or heterocyclic rings or consist of a plurality of anthraquinone units, and also vat dyestuffs of the perylene tetraearboxylic acid and naphthalene tetracar boxylic acid series, and indigoid vat dyestuffs. These dyestuffs may contain substituents of the kind usual in vat dyestuffs, for example, halogen atoms, alkoxy groups, acylamino groups or arylamino groups. In certain cases the presence of hydrophilic groups, for example, carboxylic acid groups or more especially sulfonic acid groups or sulfate groups, may be of advantage.

The invention also provides a process for the manufacture of vat dyestuffs of the above Formula 1, wherein a vat dyestufi containing at least one acylatable amino group, or an intermediate product which contains at least one 3,126,382 Patented Mar. 24, 1964 (C 0 Cl),

or 2, the condensation being carried out that the resulting product contains at halogen atoms in the 2:4:6-trichlorpyrimidine, 2:4:5:6-tetrachlorpyrimidine, 2:4-dichloro 6-methylpyrimidine, 2:4-dichloro-S-nitropyrimidine, 2:4-dichloro-5-nitro-6-methylpyrimidine, 2:4:6-trichloro-S-nitropyrimidine, and also the acid chlorides of the condensation products of one molecular proportion of one of the aforesaid halogen-pyrimidine derivatives with one molecular proportion of 3- or 4-amino-benzoic acid or S-amino-isophthalic acid, for example, the chlorides of the following carboxylic acids: 2-(3'- or 4-carboxyphenylamino)-4:6-dichloropyrimidine, 2(3'- or 4'-carboxyphenylamino)-4:5:6-trichloropyrimidine 01-h darn-Q0 0 on There may be mentioned, for example, 1-aminoanthraquinone, or 1-- pecially 1-amino4- or -5- or -8-'benzoyl amino anthraquior steaming of the dyestuff. The most favourable condinoncs. The latter may be substituted in the benzoyl tions can easily be determined by preliminary tests. radical, for example, by a halogen atom or a methoxy, The dyeings and prints produced with dyestuffs of this alkyl, trifiuoromethyl, sulfonamide or sulfone group. invention are distinguished by their excellent fastness to There may also be mentioned 1:4-diamino anthraquinone 5 light and properties of wet fastness. and 2-substitution products thereof, 1:5- or 1:8-diamino In view of the fact that the dyestuffs, in contradtstincanthraquinone and 1:5-diamino-4z8-dihydroxy anthraquition to the conventional vat dyestuffs are generally sub none. stantially irremovable from the fiber by means of hot di- The radical A in the above Formula 2 also includes methyl-formamide, it must be supposed that the dyestuff anthraquinone radicals which contain fused-on carbocyclic 10 is chemically bound to the fiber.

or heterocyclic rings, 4-amino anthraquinone-2:l(N)-acri- The dyeings produced with the dyestuffs of this invendone, S-amino-l:9-isothiazole-anthrone, 4 or S-aminoantion are, therefore, fast to dry cleaning and fast to migrathrapyrimidine, amino-acedianthrones, 4- or S-amino-l'zltion. Fabrics dyed with these dyestuffs can therefore be dianthrimide-carbazole, 4- or 5-arnino 5-benzoylaminocoated with synthe ic resins, f r ex mple, polyvinyl chlodianthrimide-carbazole, 4 amino-4 benz0ylamin0-dianride, without the dyestuff migrating into the synthetic thrimide-canbazole or 4:4'- or 5:5'-di-amino-1:l'-dianthri resin, which is especially important for the production of mide-carbazole, 4-aminoanthrapyridones, aminodibenzanartificial leather.

throne, aminoisodibenzanthrone, aminoanthranthrone, The following examples illustrate the invention, the aminobenzanthrone, aminoflavanthrone and the comparts and percentages being by weight, unless otherwise pound of the general formula stated, and the relationship of parts by weight to parts by Example 1 f F O A suspension of 3.1 parts of 2-(3'-carboxyphenyla- T mino)-4:6-dichloropyrimidine in 100 parts of dry nitrofi C benzene is treated with 2 parts of thionyl chloride and converted into the corresponding carboxylic chloride by heating for 2 hours at 95 C. 2.3 parts of 5:5'-diamino- Y 1:l-dianthrimidecarbaz0le are then stirred into the solution and the whole is heated for 4 hours at 140 to 145 C. and then for 2 hours at 170 to 175 C. After cooling, the dyestufi of the formula There are advantageously used compounds which contain is filtered off, washed with nitrobenzene and then with 3 to5 fused-on rings. alcohol, and dried in vacuo at to 60 The reaction of the aforesaid amino-compounds with When dry, the resulting dyestufif forms a brown powder the pyrimidine derivatives of the Formula 3 is advantawhich dyes cotton and regenerated cellulose from a hydrogeously carried out in an inert organic solvent, for exam- 50 sulfite vat yellowish brown shades of very good fastness ple, nitrobenzene, chlorobenzene or ortho dichloroproperties, more especially good fastness to solvents. benzene at a raised temperature. The molecular propor- The dyestulf is fixed on the fiber so securely that even tions of the components are advantageously so chosen when the dyeing is treated with a hot organic solvent such that one molecular proportion of the compound of the as dimethyl-formamide or pyridine its tinctorial strength Formula 3 is used for each amino group present in the is not substantially impaire vat dyestuff or intermediate product used as starting ma- When in this example 5 :5-diamino-1:1-dianthrimideterial. carbazole is replaced by 2.3 parts of 4:4-diamino-l:l-di- The dyestuffs 80 Obtained n be s t fr m the a anthrimidecarbazole, a dyestuff is obtained which gives tion medium and worked up into useful dry dyestufl olive dyeings of equally good properties. preparations, notwithstanding the presence of exchange- The 2-(3' carboxyphenylamino)-4:6-dichloropyrimiable halogen aioms- The dyestuffs are advantageously dine used in this example can be prepared in crystalline isolated by filtratlon- The fillfifed dystllfis y be dried, form, for example, by heating an aqueous-alcoholic soluif desired after the addition of an extender having a tion of 50% stren th of molecular proportions of h neutral or weakly alkaline reaction Advantageously the sodium salt of 3-ammobenzoic acid and 2 4 6-tr1chl0rodrying is carried out at not too high a temperature and, pyrimidine for 4 h u at t C,

invention are suitable for dyeing a very wide variety of Example 2 materials and especially for dyeing or printing textile materials of natural or regenenated cellulose by the usual -l Parts Of YP Y dyeing or printing methods used for vat dyestuffs. 70 pyrimidine are suspended with stirring in parts of dry As the reactivity of the halogen atom or atoms in the nitrobenzene and converted into the correspondin carpyrimidine ring may vary from dyestuff to dyestuif it is of boxylic acid chlor de with 2 parts of thionyl chloride advantage to select the dyeing conditions accordingly, with addition of 0.1 part of anhydrous pyridine, by heatpecially the concentration of the alkali and of the reducing ing for 2 hours at 90 to C. The excess thionyl chloagent, and the duration and temperature of the dyeing 75 ride is then removed from the clear solution in vacuo,

3,128,382 r s a and 2.9 parts of the finely powdered intermediate of the When in this example the 6.9 parts of 1 amino-4-benformula zoyl-aminoanthraquinone are replaced by an equal amount are then added. While stirring the mixture it is heated for 4 hours at 140 to 150 C. and then for another 6 hours at 170 to 180 C. After cooling, the red suspension of the new dyestufi of the formula of 1-amino-5-benzoylaminoanthraquinone or by an equimolecular amount of 1-amin0-6:7-dichloroanthraquinone, yellow dyestuiis having similar properties are obtained.

HO N H is filtered and the iilter residue is washed with nitro- Example 4 ggnzeie and then with methanol, and dried 1n vacuo at 40 2 of z (3, carboxyphenylanfino) 4:6 dich10m From an alkaline hydrosulfite vat the dyestufi dyes fig i fig gz ggggi ii f fifii i i yg g cotton and regenerated cellulose clear red shades having l 1 1. S o 1011 c y Ver God To mes of fastness heating for 2 hours at 90 to 95 C. The excess thionyl g g f, fiarboxyphenylan'finowl 6 dicmoropyrimi chloride is then removed rfirom the solution, whereupon dine used in this example can be prepared in crystalline 5 gi z g tig gggifzg g gggg i gi z i 22 9 3 form by heating an aqueous-alcoholic solution of d h o l a O strength of molecular proportions of the sodium salt of gi g g igg g ig g (to 20 The prechpltated 4-aminobenzoic acid and of 2:4:6-trichloropyrimidine for several hours at to C.

50 CH Example 3 N/ N 01 6.3 parts of 2-(3' carboxyphenylamino)-4:6-dichlorol A pyrimidine in 100 parts of dry nitrob'enzene are converted with 4 parts of thionyl chloride into the corresponding r 1H1 ture for 2 hours at to C. 6.9 parts of l-amino- 4-benzoylaminoanthraquinone are then added and the l mixture is heated with stirring to to C. After cooling to room temperature, the dyestufi? of the formula 60 CH carboxylic acid chloride by thoroughly stirring the miX- J;

is filtered off, washed with a small amount of nitrobenzene O and then with alcohol, and dried in vacuo at 45 to 50 C. H The dystufi so obtained dyes cotton and regenerated NH C \C C1 cellulose from a hydrosulfite vat yellow shades having N B 65 good f astness properties, above all good :Eastness to solvents. Y I 01 Example 5 O NH OC While being stirred, a suspension of 3.1 parts of 2-(4'- oanboxyphenylamino) 4:6-dichloropyrimidine in 100 is filtered off, washed with a small amount of nitroben- 70 parts of dry nitrobenzene is treated with 2part-s of thionyl zene and then with alcohol, and dried in vacuo at 50 C. chloride and then with 0.1 part of pyridine and converted The resulting dyestufi forms in the dry state a red into the corresponding carboxylic chloride by heating fo-rZ powder which dyes cotton and regenerated cellulose from hours at 95 C. 2.3 parts of 4:4-diamino-1:1'-diantha hydrosulfite vat orange-red shades having very good rimide-carzabole are then stirred in, another 0.1 part of fastness to light. 75 pyridine is added, and the whole is heated for 4 hours 7 at 140 to 145 C. and then for 6 hours at 170 to 180 C. After cooling, the dyestutf of the formula NH 0 I C ll or e 1') (i y NE HN HG ii g I i and CHN 0 OGQ-NH-d is filtered off, washed with nitrobenzene and then with alcohol, and dried in vacuo at 50 to 60 C.

The resulting dyestuff dyes cotton and regenerated cellulose from an alkaline hydrosulfite vat olive shades having very good properties of fastness.

Example 6 6.2 parts of 2-(4'-carboxyphenylamino)-4:6-dichloropyrimidine in 100 parts of dry nitrobenzene are converted into the carboxylic acid chloride with 4 parts of thionyl chloride by stirring and heating at 90 to 100 C. 0.1 part of pyridine and then 6.8 parts of 4-aminoanthraquinone-2:l(N)-acridone are added and the mixture 1s condensed for 2 hours at 120 to 125 C. and then for another hour at 145 to 150 C. After cooling, the dyestulf of the formula is filtered off, washed with nitrobenzene and then with alcohol, and dried in vacuo at 50 C.

The resulting dyestuff dyes cotton and regenerated cellulose from a hydrosulfite vat greenish blue shades having good properties of fastness.

Example 7 As described in Example 5, 3.1 parts of 2-(4'-carboxyphenylamino)-4:6-dichloropyrimidine in 100 parts of nitrobenzene are converted into the car boxylic acid chloride with 2 parts of thionyl chlonide and 0.1 part of pyridine. 4.2 parts of aminoacedianthrone are then stirred in and the mixture is condensed for 3 hours at 140 to 150 C. After cooling, the brown dyestuff suspension is filtered, and the dyestulf is washed with nitrobenzene and then with alcohol, and dried in vacuo at 60 C.

The dyestuff of the formula dyes cotton and regenerated cellulose vivid brown shades having very good properties of fastness.

Example 8 -in vacuo at 60 to 70 C.

The dyestuff of the formula dyes cotton and regenerated cellulose from an alkaline hydrosulfite vat brown shades which are fast to light and washing.

The aminoacedianthronesulfonic acid used in this example can be prepared as follows: Aminoacedianthrone is dissolved in 5 to 10 times its own weight of sulfuric acid of strength, and the solution is heated within one hour to C. It is stirred for another 5 hours at 190 C., allowed to cool, poured over ice, and the aminoacedianthrone-sulfonic acid so formed is filtered off, washed with sodium chloride solution until it is neutral and dried.

Dyeing method.--0.l5 part of the dyestulf prepared as described in this example are dissolved in 50 parts of Water at 60 C. The solution is poured into a solution, heated at 60 C., of 2 parts by volume of sodium hydroxide solution of 36 B. and 1.2 parts of hydrosulfite in 350 parts of water. In the resulting dyebath 10 parts of cotton are dyed for 45 minutes with addition of 12 parts of sodium chloride while allowing the temperature of the dyebath to rise to 80 C. The dyed cotton is rinsed in flowing cold water to complete its oxidation, then acidified and soaped at the boil.

SOsII Examples 9 to 18 By acylating the starting products listed in Column II of the following table with the carboxylic acid chloride of the carboxylic acid shown in Column III, further dyestuffs are obtained which dye cotton the shades shown in Column IV.

I II III IV C O C O i 2- (3-cardoxyphenorange- 17 C=C y1amiu0)-4:6- red.

\ NH2 dichloropyrimidine. S

fl) NH:

18 .do Do.

I l O NH-O C- -Cl Example 19 is filtered off, Washed with a small amount of nitrobenzene and then with alcohol, and dried in vacuo at 70 C.

The resulting dyestuff dyes cotton and regenerated cellulose orange-yellow shades having good properties of fastness.

When tetrabromopyrimidine is used instead of tetrachloropyrimidine a dyestuff having similar properties is obtained. Example 20 7.6 parts of 2 (3' carboxyphenylamino)-4:5:6-trichloropyrimidine in 100 .parts of dry nitrobenzene are converted into the corresponding carboxylic acid chloride with 4 parts of thionyl chloride by heating for 2 hours at 90 to 95 C. with thorough stirring. 6.9 parts of 1-amino S-benzoylamino-anthraquinone are added and the whole is heated to 125 to 130 C. and stirred on for 3 hours at the same temperature. After cooling to room tem perature, the yellow dyestufi of the formula is filtered off, washed with a small amount of nitrobenzene and then with methanol, and dried in vacuo at 60 C.

The 2- 3 -carboxyphenylamino -4 5 6-trichloropyrimidine used in this example can be prepared, for example, by heating an aqueous-alcoholic solution of 50% strength of molecular proportions of the sodium salt of 3-aminobenzoic acid and of 2:4:5:6-tetrachloropyrimidine for 4 hours at 70 to 75 C.; the product is obtained in the form of colorless needles melting at 203 to 205 C.

14 parts of the dyestuff prepared as described in paragraph 1 above are finely ground in a ball mill with 126 parts of a neutral solution of 125 parts of dinaphthylmethane-disulfonic acidin 1000 parts of water.

A suspension of 7.5 parts of the resulting paste in 250 parts of warm Water is added to a solution, heated at 50 C., of 10 parts by volume of sodium hydroxide solution of 30% strength and 6 parts of sodium dithionite in 1750 par-ts of water and the whole is vatted for one minute. 50 parts of cot-ton are dyed in the resulting dyebath for 45 minutes at 50 to 60 C. with addition of 60 parts of sodium chloride. The dyed cotton is rinsed, oxidised, acidified, once more thoroughly rinsed, and soaped at the boil. A clear yellow coloration is obtained, when coating polyvinyl chloride, which possesses very good fastness to solvents and migration.

Example 21 3.8 parts of 2 (4' carboxyphenylamino)-4:5:6-trichloropyrimidine in parts of dry nitrobenzene are converted into the corresponding carboxylic acid chloride with 2 parts of thionyl chloride by heating for 2 hours at to C. with stirring. 3.45 parts of l-amino-S- benzoylaminoanthraquinone are added and the mixture is heated to to C. and stirred at the same temperature for 3 hours longer. After cooling to room temperature, the dyestutf of the formula is filtered off, washed with nitrobenzene and then with alcohol, and dried in vacuo at 60 C.

The resulting dyestuff dyes cotton and regenerated cellulose pure yellow shades of very good fastness properties, and when used for coating polyvinyl chloride it produces colorations of good fastness to solvents and migration.

The 2- (4'-carboxyphenylamino) -4 5 6-trichloropyrimidine used in this example can be prepared, for example, by heating an aqueous-alcoholic solution of 50% strength of molecular amounts of the sodium salt of 4-aminobenzoic acid and of 2:4:5 :6-tetrachloropyrimidine for 4 hours at 70 to 75 C.; the product is obtained in colorless needles melting at 250 to 252 C.

What is claimed is:

1. A vat dyestuff of the formula 13 14 wherein Z is a member selected from the group consisting of H and Cl, and A is a member selected from the group consisting of NH 0 NH 1} ll u u I o1 I 1] I H- 0 0 N C O L ATE-( (3-01 0 II H H I Li 1" ll '0' 1 mu /k l: N \N 0 NH 43-01 o o a OT I] ll 0 o HN-fi 0-01 N 11 /r\ I \C% o l I (i NH-OC-O c0 00 OCHN o s s T? c1 A I I El NH N f Q Y I I 16 4. The dyestuff of the formula F i ll I Cl-C /c-c1 y) NH 00 3 01 5. The dyestulf of the formula 0 NHOC-- I I 1111i 0 NIH-00G I H N fi NH G 6. The dyestufi of the formula U I GO l NH-CO- c -NH(|3 c-c1 SOaH I N\ 0-01 H I II \C/ O A n x being a whole number from zero to one and being zero when A is one of the last two mentioned members. 6

2. The dyestufl? of the formula 0 0 II If G\ c\ HN -N +=O \C +=O l 01-0 c 1-'n1 HN-(fi (l3Ol Eh 1 N 011 3. The dyestufi of the formula 0 NH O I 31 (I11 0 A 0 \N NH EN 0 3,126,382 17 i8 7. The dyestufl of the formula References Cited in the file of this patent UNITED STATES PATENTS 1,888,631 Kunz et a1 Nov. 22, 1932 2,731,464 Ebel et a1 Jan. 17, 1956 3,042,475 Heslop et a1. July 3, 1962 FOREIGN PATENTS 91,206 Norway Mar. 17, 1958 STATES PATENT OFFICE v l .A CERTIFICATE OF CORRECTION r Patent No, 3,126,332 March 24,. 1964' v Q I Max St aeuble I I Q I It is hereby certified that error appears in the above numbered patent requiring correction and that the said Letters Patent should read as corrected below.

Columu 5 lines 6l to 69, for the right-hand-portioh of the formula'reading:

I v C -Cl -C C-Cl I read N /CH 7 N /CH A o column 6, line 62, for "dystuff" read dyestuff column I 8, lines 30 to 43, the formula should appear as shown below instead of as in the patent:

column 11, in the table, under the heading "III", line 1 thereof for "2-(3 cardoxyphen-" read 2-(3 carboxyphencolumn 12, lines 45 to 53, Example 21, for the upper left-hand portion of the formula reading:

read

-NH O column 13, lines 51 to 58, the fifth formula, for the right-hand portion of the formula reading:

read

HN O HN O Signed and sealed this 22nd day of December 1964.

(SEAL) Attest:

ERNEST W. SWIDER EDWARD J. BRENNER Attesting Officer Commissioner of Patents 

1. A VAT DYESTUFF OF THE FORMULA 